Parasiticide



Patented May 12, 1942 2,282,907 PARASITICIDE William P. ter Horst,PackanackLake, N. 1., as-

signor to United States Rubber Company, New

York, N. Y., a corporation of New Jersey No Drawing. Application May 1,1941, Serial No. 391,347

13 Claims. (Cl. 167-33) This invention relates to chemicals foundsuitable as parasiticides, for example as fungicides, bactericides,insecticides, fumigants, etc.

This application is a continuation-in-part of my application Serial No.234,955, filed October 14, 1938.

More particularly, the invention relates to the preparations that areprepared to contain the chemicals as essential active constituents, forthe purpose of combatting germs, bacteria, fungi, or insects, as well asto materials treated with the chemical for the same purpose. Further, aprincipal object of the invention is to preserve rubber latices with theaid of said chemicals.

The chemicals are termed biocides since they are toxic or repugnant tovarious living organisms of low orders of life. The chemicals arealpha-ar yl beta-amino-ethanes and subscribe to the general formula R-CO-CHC Hz-Y ,L where R is an aryl or a chloro-aryl group; R is hydrogenor alkyl; and Y is the residue of an amine from the class consisting ofprimary and secondary amines, said amine residue being joined to theadjacent methylene group through the amine nitrogen atom. Preferably, Yis the residue of a secondary heterocyclic amine. The chemicals may beused as such, or in the form of their salts, particularly their watersoluble salts, for example, the hydrochloride, sulphate, arsenate,borate, salicylate, tannate, thiocyanate, laurate, oleate, etc. Thechemicals may be used in the form of sprays or dusts, either alone or incombination with other biocides, or with inert materials, diluents orsolvents, or with auxiliary ingredients such as wetting agents, stickingagents, spreading agents, or the like.

The chemicals may be prepared by the wellknown Mannich type of reaction,from an alkyl aryl ketone, formaldehyde, and an amine or amine salt; forexample, the hydrochloride of alpha-benzoyl beta-piperidino-ethane maybe prepared by heating under reflux, during three 'ljours, equimolecularquantities of acetophenone, paraformaldehyde dissolved in water, andpiperidine hydrochloride. The free amine (B. P. 139- 141 C. at 18 mm.mercury pressure) can be recovered by treatment of the reaction product,with caustic alkali. Alpha-benzoyl beta-morpholino-ethane (B. P.157-163 C. at 23-24 mm. mercury pressure) may be prepared similarly frommorpholine hydrochloride. In place of acetophenone, other alkyl arylketones having a tion, such a propiophenone or ethyl phenyl ketone,propyl phenyl' ketone, p-chloro-acetophenone, and methyl naphthylketone. For example,

alpha-p-chlorobenzoyl beta-piperidino ethane (melting point 193-194 C.)may be prepared from p-chloroacetophenone, paraformaldehyde, andpiperidine hydrochloride.

The amino group at Y in the above formula may correspond to any of thefollowing amines or their salts, after removal of replaceable hydrogenattached to the amine nitrogen atom: dimethylamine, diethylamine,dipropylamine, dibutylamine, diphenylamine, dicyclohexylamine,diamylamine, aniline, dibenzylamine, monobenzylamine, phenetidine,diphenylguanidine, morpholine, diethanolamine, piperidine, pipecoline,etc.

The following examples are given to illustrate the invention: v

EXAMPLE 1,-Fungicz'dal action.Test organism, Macrosporium Sarcinaeforme.Concentra tion of chemicals, 5 grams per liter of water, in the presenceof a small amount of sulfite lye as a wetting agent or of Wetanol, acommercial wetting agent.

The chemicals were sprayed onto a glass slide, and the sprayed film wasdried in air. On each slide then was placed approximately 6,000 sporesof the fungus Macrosporium Sarcinaeforme in a drop of water and thespores were permitted to germinate in moist chambers at 25 C. during12-18 hours. My tests show that at a concentration of 5 grams per literof water, alphabenzoyl beta-piperidino-ethane CHI-CH2 and alpha-benzoylbeta-morpholino-ethane prevented spore germination completely.

EXAMPLE 2.Insecticz'dal actz'o11 .-The same two compounds as referred toin Example 1 are toxic towards the Colorado potato beetle when appliedin the form 'of a 10% emulsion in water, causing stupefaction in 45minutes and death in 2 hours.

cyclohexylamine,

. emulsion was made comprising as illustrated by the chemicals; in

ExAmP'La 3.A solution was prepared, comprising 10% of alpha-benzoylbeta-piperldinoethane, 1% of Emulphor EL" (a commercial wetting agent),and 89% of white oil. A water 1 part of the above solution and 100 partsof water. The emulsion was sprayed upon Golden Gleam Nasturtium leavesupon which black bean aphids (Aphis rumicis) had been placed. Out of 478aphids,

4'75 died within 24 hours. which is equivalent to a mortality of 99.3%.

Alpha-benzoyl beta-piperidino-ethane is high ly toxic to meal wormlarvae. The two compounds mentioned in Example 1 may also be used asfumigants. Solutions of these compounds, when applied as mist, haveshown great toxicity to black carpet beetle larvae.

Compounds such as C -CHr-CHa-Y where Y is the residue of a secondaryheterocyclic amine joined to the adjacent methylene group through theamine nitrogen atom, or their salts, Example 1, and theirhydrochlorides, etc.,' are especially useful in the preservation ofrubber latex, natural as it comes from the tree, or containing wellknownalkaline preservatives such as ammonia, sodium or potassium hydroxide,or water-soluble organic derivatives of ammonia, for example basicamines, such as the mono-, diand trialkyl amines.

The closed nitrogemring compounds inhibit bacterial growth in the latex,when used in amounts as low as .02% by weight, thereby preventingincrease in KOH number due to formation of acidic products of bacterialdecomposition. Proportions in excess of .2% by weight are usuallyunnecessary.

Their use in alkaline-preserved latex permits a reduction in the usualamount of alkaline preservative to amounts as low as .1% in the case ofammonia, and generally in the range of .2 to 175% ammonia. Theeffectiveness of the chemicals in latex is shown by the followingexamples:

EXAMPLE 4.-.1% of alpha-benzoyl beta-piperidino-ethane was added to anammonia latex containing approximately .1% ammonia and having a pH of8.77. A control sample of latex at the same pH, containing ammonia, wasalso set up. The control sample became putrid within five days andcoagulated within 24 days, while the sample preserved with thealpha-benzoyl beta-piperidinoethane was sweet and fluid at the end of 60days.

EXAMPLE 5.-.2% of alpha-benzoyl beta-morpholino-ethane was added to anammonia latex containing approximately .1% ammonia and having a pH of8.25; at the same time a control containing no alpha-benzoylbeta-morpholinoethane was set up. The control was hours and coagulatedin 48 hours, while the sample containing alpha-benzoylbeta-morpholinoethane was still fluid and sweet at the end of sixmonths.

In both examples 4 and 5, the latex samples had been inoculated with avery powerful strain of latex bacteria.

EXAMPLE 6.Commercial latex, containin 38.6% solids, and having a KOHnumber of 1.64, ammonia 38%, and a pH of 9.75, was treated with .1% ofthe hydrochloride of alpha-benzoyl putrid in 24 V Bacteria par cc.

6 days 30 days Control 1,000, 000 1,000,000 .l% hydrochloride ofnlpha-benzoyl betapiperidino-ethanc 1,000 0 Similar results are obtainedby the use of alpha-p-chlorobenzoyl beta-piperidino ethane or its saltssuch as the hydrochloride.

It is obvious that various modifications will suggest themselves topersons skilled in the art and it is not desired to limit the inventionotherwise than as set forth in the appended claims.

Having thus described my invention, what I claim and desire to protectby Letters Patent. is:

1. An insecticide, fungicide and germicide preparation containing as anactive constituent,

an alpha-aroyl beta-amino-ethane compound selected from the classconsisting of chemicals of the formula R-CO-CH (R' --CHz-Y where R is anaryl or chloroaryl group; R is hydrogen or alkyl; and Y is the residueof an amine from the class consisting of primary and secondary amines,said amine residue being joined to the adjacent methylene group throughthe amine nitrogen atom, and water-soluble salts of such chemicals.

2. An insecticide, fungicide and germicide preparation containing as anactive constituent, an alpha-aroyl beta-amino-ethane compound selectedfrom the class consisting of chemicals of the formula where R is an arylor chloroaryl group; and. Y is the residue of an amine from the classconsisting of primary and secondary amines, said amine residue beingjoined to the adjacent methylene group through the amine nitrogen atom,and water-soluble salts of such chemicals.

3. An insecticide, fungicide and germicide preparation containing as anactive constituent an alpha-benzoyl-beta-piperidino ethane.

4. An insecticide, fungicide and germicide preparation containing as anactive constituent an alpha-benzoyl-beta-morpholino-ethane.

5. An insecticide, fungicide and germicide preparation containing as anactive constituent an alpha-chlorobenzoyl beta-piperidino ethane.

6. An insecticide, fungicide and germicide preparation containing as anactive constituent a product having the general formula C O-GHz-ClIr-Ywhere Y is the residue of an amine from the class consisting of primaryand secondary amines, said amine residue being joined to the adjacentmethylene group through the amine nitrogen atom.

7. A latex preservative comprising an alphaaroyl beta-amino-ethanecompound selected from the class consistingof chemicals of the for mulaRCOCH2CH2Y where R is an aryl or chloroaryl group, and Y is the residueof a secondary heterocyclic amine Joined to the adjacent methylene groupthrough the amine nitrogen atom, and water-soluble salts of suchchemicals.

8. Latex containing an alpha-aroyl beta-amino-ethane compound selectedfrom the class consisting of chemicals of the formula R'COCH2-CH2Y whereR is an aryl group, and Y is the residue of a secondary heterocyclicamine joinedto the adjacent methylene group through the amine nitrogenatom, and water-soluble salts of such chemicals.

10. Latex containing an alpha-benzoyl-betapiperidino ethane compound.

11. Latex containing an alpha-benzoyl-betamorpholino ethane compound.

12. Latex containing an alpha-chlorobenzoyl beta-piperidino ethanecompound.

13. Latex containing an alpha-aroyl beta-amino-ethane compound selectedfrom the class consisting of chemicals of the formula 010-0 o-cm-c Hr-Ywhere Y is the residue of a secondary heterocyclic amine joined to theadjacent methylene group through the amine nitrogen atom, andwater-soluble salts of such chemicals.

' WILLIAM P. m HORST.

